JP2011078886A - Trichlorobenzene-containing liquid treatment method and apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and apparatus which inject stoichiometrically required ozone to wastewater containing trichlorobenzene discharged from chemical industry, industrial waste treatment industry and the like, and wastewater or groundwater containing trichlorobenzene, supply them to a high silica zeolite adsorbent, capable of absorbing trichlorobenzene and ozone and treat the trichlorobenzene with high efficiency by ozone adsorption reaction. <P>SOLUTION: As trichlorobenzene is a hardly biodegradable compound, its bioactive treatment is difficult, and its adsorption removal by activated carbon or the like consumes a large amount of adsorbent to increase cost. The stoichiometrically required ozone is injected to the wastewater or groundwater containing trichlorobenzene, and then the wastewater or groundwater is supplied to the high silica zeolite adsorbent 6a which adsorbs trichlorobenzene and ozone to treat the trichlorobenzene with high efficiency by the ozone adsorption reaction. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method and apparatus for detoxifying a liquid containing trichlorobenzene discharged from a chemical factory or the like, and more particularly to a method and apparatus for detoxifying a trichlorobenzene-containing liquid with improved detoxification efficiency by ozone.

One of the detoxification methods for contaminated liquids containing trichlorobenzene is biologically active treatment, but it depends on the biochemical reaction, so the treatment speed is slow, and it is necessary to maintain a microorganism tank that decomposes trichlorobenzene. Requires great care and experience and is not practical. An oxidation method using ozone has also been attempted, but it has not been adopted because the reaction rate between low-concentration trichlorobenzene and ozone is not so high. However, since ozone undergoes self-decomposition, there is little risk of remaining in the treatment liquid and affecting the human body, and it is expected that the field of use will expand further in the future as a clean treatment agent. If it can be used as an agent, it is expected as a very effective treatment method.
Treatment with ozone is performed by injecting an ozone-containing liquid from an ozone generator (ozonizer) into the trichlorobenzene-containing liquid. Usually, however, the concentration of trichlorobenzene in the liquid is very dilute. There is also a problem that the proportion of ozone that decomposes before contributing to decomposition is large, and the detoxification efficiency is low.

Adsorption Society of Japan 2000 Annual Meeting “Adsorption and Desorption Characteristics of Dissolved Ozone in Water in Silica Adsorbent” Motoyuki Suzuki et al.

  The present invention solves such a problem in the prior art, and a trichlorobenzene-containing liquid treatment method capable of efficiently treating a liquid containing trichlorobenzene using ozone, which is a highly safe oxidizing agent, and therefore An object of the present invention is to provide a device.

The present invention adopts the following configurations (a) to (d) as means for solving the above-mentioned problems.
(A) (A) Add and mix ozone into the trichlorobenzene-containing liquid,
(B) The contained liquid adsorbs ozone and adsorbs trichlorobenzene (1) pentasil zeolite, (2) zeolite β, (3) ultrastable Y-type zeolite (USY), (4) mesoporous silicate, (5) flowing through a packed tower packed with at least one adsorbent selected from the group of ultrastable mordenite (USM);
(C) detoxify trichlorobenzene in the liquid by the action of ozone;
A method for treating a trichlorobenzene-containing liquid.
(A) (D) The method for treating a trichlorobenzene-containing liquid as described above, wherein the treatment liquid obtained by detoxification in (C) is brought into contact with an ozone decomposing agent to decompose residual ozone.
(C) Adsorbs ozone and adsorbs trichlorobenzene (1) Pentasil zeolite, (2) Zeolite β, (3) Ultrastable Y-type zeolite (USY), (4) Mesoporous silicate, (5) Ultrastable An adsorbent packed tower provided with at least one adsorbent layer selected from the group of mordenite (USM), a supply pipe for supplying a liquid containing trichlorobenzene to the adsorbent packed tower, and connected to the supply pipe An apparatus for treating trichlorobenzene-containing liquid, comprising: an ozone generator for adding ozone to the liquid; and a discharge pipe for discharging the treated liquid from the adsorbent packed tower.
(D) The apparatus for treating a trichlorobenzene-containing liquid as described above, wherein an ozone decomposing agent layer for decomposing ozone leaking is provided on the downstream side of the adsorbent packed tower.

  According to the method of the present invention, in the treatment of trichlorobenzene-containing liquid with ozone, the effective utilization rate of ozone is improved by using an adsorbent that efficiently adsorbs ozone and adsorbs trichlorobenzene, and the treatment speed is increased. Fast and efficient wastewater treatment becomes possible. In addition, the amount of leaked ozone in the discharged processed liquid is small because the ozone utilization rate (the rate contributing to the oxidation of trichlorobenzene, etc.) is improved and the ozone adsorption power of the adsorbent used is high. Furthermore, ozone leakage can be completely prevented by providing an ozone decomposing agent layer such as activated carbon if necessary. Moreover, according to the apparatus of this invention, the process by the ozone of the liquid containing a trichlorobenzene can be performed efficiently at a low operating cost.

It is the schematic which shows an example of the processing flow of this invention. It is a graph which shows the relationship between SV value and a trichlorobenzene removal rate in Example 2. FIG. 6 is a graph showing the relationship between the ozone / treatment substance molar ratio and the trichlorobenzene removal rate in Example 3.

In the present invention, (A) ozone is added to and mixed with the trichlorobenzene-containing liquid, and (B) the above-described liquid is passed through a packed tower packed with a specific adsorbent that adsorbs ozone and adsorbs trichlorobenzene. (C) Trichlorobenzene in the liquid is rendered harmless by the action of ozone.
As the trichlorobenzene-containing liquid, wastewater containing high-concentration trichlorobenzene corresponding to the COD regulation value specified by the Ministry of the Environment is targeted.
As an ozone generator (ozonizer) for supplying ozone, any known system such as silent discharge system, ultraviolet lamp system, water electrolysis system, etc. can be applied. As a method of adding ozone, there are a method of sucking ozone into an ejector disposed upstream and mixing it with a treatment liquid, and a method of generating microbubbles with an ozone diffuser tube inserted in a liquid phase and injecting it by gas-liquid contact. It is common. The amount of ozone added may be appropriately set depending on the type, concentration, etc. of trichlorobenzene in the treatment liquid, but in normal sewage liquid treatment, it is 1 to 20 moles, preferably about 3 to 10 moles per mole of trichlorobenzene. is there.

The adsorbent used in the present invention must adsorb ozone and adsorb trichlorobenzene. Such adsorbents of the present invention include (1) pentasil zeolite, (2) zeolite β, (3) ultrastable Y-type zeolite (USY), (4) mesoporous silicate, and (5) ultrastable mordenite (USM). At least one kind.
Although the present invention is not limited by theory, the silica-based inorganic porous material having a high SiO ₂ / Al ₂ O ₃ ratio according to the present invention is stronger than an aluminosilicate conventionally used as an ozone adsorbent. Since it does not have a Lewis acid point on the solid surface, it is considered that there is little ozonolysis and high ozone adsorption capacity. This is because the ammonia β peak (high temperature peak) considered to correspond to the strong acid point in the ammonia TPD (temperature programmed desorption curve) test of the adsorbent is from an aluminosilicate having a low SiO ₂ / Al ₂ O ₃ ratio. Is based on the strong peak.
Therefore, the ozone adsorbent of the present invention simultaneously adsorbs ozone and trichlorobenzene, concentrates ozone and trichlorobenzene, and adsorbs ozone without being decomposed within the crystal structure of the adsorbent, thereby efficiently oxidizing trichlorobenzene. Has the effect of being decomposed.
As described above, the adsorbent of the present invention has a high ozone adsorption capability, a low decomposition rate of the adsorbed ozone, and a property of adsorbing trichlorobenzene, and thus can be stably treated in the liquid phase.

Pentasil-type zeolite (S-5)
Among the ozone adsorbents used in the present invention, the pentasil-type zeolite is known as ZSM-5, silicalite. A pentasil zeolite having a SiO ₂ / Al ₂ O ₃ ratio of 100 or less is referred to as ZSM-5, and a SiO ₂ / Al ₂ O ₃ ratio having a SiO ₂ / Al ₂ O ₃ ratio of 100 or less is referred to as silicalite.
The SiO ₂ / Al ₂ O ₃ ratio of the pentasil-type zeolite of the present invention is preferably 20 to 1000, more preferably 20 to 200. In the case of a pentasil-type zeolite having a SiO ₂ / Al ₂ O ₃ ratio of less than 20, the ozonolysis becomes significant, so that the oxidation reaction efficiency of trichlorobenzene decreases. On the other hand, if it exceeds 1000, the cost of synthesis increases greatly. Absent.

Zeolite β (S-4)
The SiO ₂ / Al ₂ O ₃ ratio of the zeolite β of the present invention is preferably 20 to 1000, more preferably 20 to 200. Ozone decomposition is remarkable in zeolite β having a SiO ₂ / Al ₂ O ₃ ratio of less than 20, so that the oxidation reaction efficiency of trichlorobenzene decreases. On the other hand, if it exceeds 1000, the cost of synthesis is greatly increased, which is not common. .
Super stable Y-type zeolite (S-3)
Among the ozone adsorbents used in the present invention, ultra-stable Y-type zeolite (hereinafter, USY: Ultra Stable Y Type zeolite) is obtained by converting a Y-type zeolite having a SiO ₂ / Al ₂ O ₃ ratio of 5 prepared by hydrothermal synthesis to a temperature of 120. A Y-type zeolite having a high SiO ₂ / Al ₂ O ₃ ratio was prepared by removing aluminum in a Y-type zeoirate (faujasite) crystal structure by contacting with water vapor at a temperature of at least ° C.
_SiO 2 / _Al 2 _{O 3} ratio of USY of the present invention is preferably 20 to 1000, more preferably from 20 to 200. In USY having a SiO ₂ / Al ₂ O ₃ ratio of less than 20, ozonolysis becomes prominent, so the oxidation reaction efficiency of trichlorobenzene decreases. On the other hand, when it exceeds 1000, the cost of synthesis is greatly increased, which is not common.

Mesoporous silicate (S-2)
To a water in which a solvent such as ammonium bromide, which is a tertiary ammonium salt excellent in micelle formation with monosilicic acid at a low pH, is dissolved with vigorous stirring, a silicate dissolved in water, such as sodium silicate, is added, Further, an aluminum salt dissolved in water, for example, aluminum sulfate, is added little by little to form a suspension, and the suspension is stirred. The addition, dissolution, and stirring operations are usually performed at room temperature. After the precipitate formed in the liquid is filtered to separate the porous powder, it is washed with water, placed in an electric furnace, heated to remove surface moisture, and then heated to remove the solvent by pyrolysis. To obtain mesoporous silicate. The obtained mesoporous material is a porous material (porous body) having a uniform and regular arrangement of mesopores (diameter 2 to 50 nm), and is structurally “MCM-41” (uniform mesoscopic size of 2 to 50 nm). It has a two-dimensional columnar structure that is very similar to (silica having fine pores).
The mesoporous diameter of the mesoporous silicate of the present invention is preferably 12 to 100 nm.

Super stable mordenite type zeolite (S-1)
Among the ozone adsorbents used in the present invention, ultra-stable mordenite-type zeolite (hereinafter USM: Ultra Stable Mordenite Type Zeolite) is obtained by converting a mordenite-type zeolite having a SiO ₂ / Al ₂ O ₃ ratio of about 5 prepared by hydrothermal synthesis to a temperature. A mordenite-type zeolite having a high SiO ₂ / Al ₂ O ₃ ratio was prepared by contacting aluminum vapor at 120 ° C. or higher to remove aluminum in the mordenite-type zeolite crystal structure.
_SiO 2 / _Al 2 _{O 3} ratio of USM of the present invention is preferably 20 to 1000, more preferably from 20 to 200. In USM having a SiO ₂ / Al ₂ O ₃ ratio of less than 20, ozonolysis becomes remarkable, so that the oxidation reaction efficiency of trichlorobenzene decreases. On the other hand, if it exceeds 1000, the cost of synthesis is greatly increased, which is not general.

The present invention has found that a specific adsorbent can efficiently adsorb ozone while conducting adsorption tests in the liquid phase of ozone, and that the co-adsorbed trichlorobenzene can be detoxified with ozone with high efficiency. Based on the results.
Thus, when trichlorobenzene and ozone coexist in the presence of the adsorbent of the present invention, ozone oxidation of trichlorobenzene in the liquid proceeds efficiently. Although not limiting the present invention, the following oxidative degradation mechanism is conceivable.
The ozone oxidative decomposition reaction in the liquid proceeds in proportion to the product [O ₃ ] · [TCB] of the ozone concentration [O ₃ ] and the trichlorobenzene concentration [TCB] in the liquid. On the other hand, since ozone and trichlorobenzene are selectively adsorbed on the adsorbent phase of the present invention, the ozone concentration [O ₃ ] and the trichlorobenzene concentration [TCB] on the adsorbent surface are 10 to 10 respectively compared to the simple liquid phase. It reaches about 100 times (Non-Patent Document 1). Therefore, [O ₃ ] · [TCB] on the adsorbent surface is expected to reach 100 to 10,000 times in the liquid phase.
This is a reaction on high silica zeolite,
C ₆ H ₃ Cl ₃ + 4O ₃ → CO ₂ + HCl --- 1
It was confirmed that.

The adsorbent of the present invention can be used by molding it into an arbitrary shape such as a granular shape, a pellet shape, a Raschig ring shape, or a honeycomb shape, either alone or in the form of a mixture depending on the purpose of use.
The amount of adsorbent used in the present invention varies depending on the purpose of use, but usually 1 m ³ of adsorbent under conditions of 1 to 1000 ppm (w / w) of pollutants and 1 to 10,000 ppm (w / w) of ozone. The SV value is about 1 to 250 (1 / h).
The performance of the adsorbent of the present invention varies depending on the purpose of use, but exhibits a very high removal rate of 80% or more.

  Further, in the liquid phase, ozone is frequently decomposed by collision with a third substance other than trichlorobenzene without contributing to detoxification, and there is a limit to detoxification efficiency of ozone. However, in the detoxification of trichlorobenzene by ozone on the adsorbent surface of the present invention, ozone and trichlorobenzene are selectively adsorbed on the adsorbent, so the probability of ozone decomposition due to collision with a third substance is greatly increased. The ozone is efficiently consumed for detoxification of trichlorobenzene.

Decontamination treatment of trichlorobenzene in the liquid phase In conventional methods with poor efficiency (bioactive treatment and liquid ozone reaction), the capacity of the device is large, and there is a concern that the activity may be greatly reduced due to fluctuations in the liquid composition and invasion of competing microorganisms. It always existed, and there was a strong need for improvement in terms of economy and maintainability. Wastewater treatment by homogeneous liquid phase reaction of trichlorobenzene ozone oxidation reaction is not adopted because of its very low efficiency, but it is adopted as a downstream treatment of biologically active treatment as a general reduction of COD components. However, the installation of this device upstream of the bioactivity treatment has not been adopted due to the degradation of the performance of the bioactivity tank due to leaked ozone. However, in the present invention, in the case of normal liquid treatment, unreacted ozone stays adsorbed on the adsorbent, so there is almost no risk of leakage to the downstream, and the leaked ozone concentration is 1/10 or less of the conventional. .
However, even in the present invention, when a large amount of ozone is added such as sterilization of special bacteria, or as a countermeasure when it leaks for some reason, it leaks to the treatment liquid outlet part of the adsorbent packed tower that performs detoxification treatment with ozone. Unreacted ozone can be decomposed by providing a decomposition agent layer that decomposes ozone. Examples of the ozonolysis agent include activated carbon and alumina compounds that are consumable adsorbents that come into contact with leaked ozone and are oxidized to CO ₂ themselves. The decomposing agent layer may be provided inside the outlet portion of the adsorbent packed tower, or may be provided separately outside the packed tower. In the present invention, since the leak ozone concentration is low, the durability of the ozonolysis agent can be significantly extended to about 10 times the conventional one.

  If necessary, a filter medium layer for removing dust can be provided on the upstream side of the ozone injection point into the trichlorobenzene-containing liquid and / or on the downstream side of the ozone adsorption reactor. The presence / absence, the installation position, etc. of the filter material layer may be appropriately determined depending on the state of the apparatus and the properties of the trichlorobenzene-containing liquid.

  Next, the processing apparatus of the present invention will be described with reference to the drawings. FIG. 1 shows an example of a treatment flow of a trichlorobenzene-containing liquid in which the present invention is applied to wastewater treatment from factory wastewater. In FIG. 1, the trichlorobenzene-containing liquid from the main plant 1 is sent to the mixer 4 through the drainage discharge pipe 2 by the drainage transport pump 3, and ozone is injected from the ozone generator 5 and introduced into the adsorbent packed tower 6. Is done. The adsorbent packed tower 6 is filled with the specific adsorbent of the present invention, and trichlorobenzene and ozone in the introduction liquid are co-adsorbed on the adsorbent and react in a high concentration state to decompose trichlorobenzene. . Normally, there is no leakage of ozone into the treated liquid discharged from the treatment liquid discharge pipe 7, but activated carbon or the like is disposed on the treatment liquid outlet side in the adsorbent packed tower 6 or the downstream of the adsorbent packed tower 6 as necessary. An ozonolysis agent layer may be provided. FIG. 1 shows an example in which an ozone decomposing agent layer 6b is provided on the treatment liquid outlet side of the adsorbent layer 6a in the adsorbent packed tower 6 via a partition 6c.

Hereinafter, the present invention will be described more specifically with reference to examples.
(1) pentasil zeolite (S-5), (2) zeolite β (S-4), (3) ultrastable Y-type zeolite (USY) (S-3), (5) ultrastable mordenite (USM) ( For S-1), a Zeolist powder sample was used.

On the other hand, as the mesoporous silicate, (low temperature synthesis method (4) mesoporous silicate (S-2)) was adopted. The preparation method is described below.
Cetyltrimethylammonium bromide (CTMAB; C ₁₆ H ₃₅ (CH ₃ ) ₃ NBr) (FW364.45 manufactured by Tokyo Chemical Industry Co., Ltd.) 6.0 kg of water dissolved in 32 liters of water was added tetramethylammonium hydroxide (TMAOH) aqueous solution (( CH _{3) 4} NOH, water 25 wt%) was added to 30 to 33 liters and adjusted to pH 7.7.
Vigorous stirring this, sodium silicate dissolved in water 15.4 l _{(Na 2 O · 2SiO 2 ·} 2.52H 2 O) (FW 227.56 Kishida Chemical) 3.00 kg was added, further water 31. 6 liter dissolved in aluminum sulphate _{(Al 2 (SO 4) 3} · 17H 2 O) ( Nacalai Pure chemicals) 0.01～0.25Kg added portionwise and the suspension was stirred for 3 hours at room temperature .
The precipitated product is filtered to separate the porous powder, washed with water, put in an electric furnace, first kept at 110 ° C. for about 8 hours to remove surface moisture, and then heated at a rate of 100 ° C. / About 1 kg of mesoporous silicate was prepared by heat-decomposing and removing cetyltrimethylammonium bromide by heating and heating at 600 ° C. for 6 hours. The obtained gel composition is SiO ₂ : Al ₂ O ₃ : CTMAB: H ₂ O = 0.8: 0.0012 to 0.012: 0.5: 80, and the yield of the powdered mesoporous silicate is 80 %Met.
The powdery SiO ₂ / Al ₂ O ₃ ratio prepared by the above procedure is 20 to 1000, the specific surface area measured by BET surface area measuring machine manufactured by Nippon Bell Co., Ltd. is 767 to 1100 m ² / g, and the pore diameter is 3 0.5 nm.

The adsorbent samples of the present invention are distinguished by attaching the SiO ₂ / Al ₂ O ₃ ratio at the end of S-1 to S-5 produced above. Also, unfilled and low _SiO 2 / _Al 2 _{O 3} ratio zeolite as Na-A type zeolite (hereinafter Na-A: UOP Inc. _SiO 2 / _Al 2 _{O 3} ratio of 2) as a comparative example was used. Unfilled was represented as R-1, and Na-A filled as R-2. The shape of R-2 was a monolith having a diameter of 10 cm and a height of 30 cm.
Industrial water containing 10 ppm was used as trichlorobenzene. Although trichlorobenzene has three isomers, a liquid containing trichlorobenzene containing a mixture of the three isomers was used for the test. The trichlorobenzene concentration is the total trichlorobenzene concentration.

A treatment test of the trichlorobenzene-containing liquid with ozone was performed using the flow test apparatus of FIG. 1 (no ozonizer layer was provided). Table 1 shows the adsorbents used, and Table 2 shows the test conditions.
The waste liquid containing 10 ppm of trichlorobenzene was treated under the conditions shown in Table 2, and the trichlorobenzene concentration (outlet trichlorobenzene concentration) and ozone concentration (outlet O ₃ concentration) in the liquid sampled at the portion of the treatment liquid discharge pipe 7 in FIG. ) Was measured.
The adsorbent used was (S-1-20, -200, -1000) USM, (S-2-20, -200, -1000) mesoporous silicate, (S-3-20, -200, -1000). USY, (S-4-20, -200, -1000) β, (S-5-20, -200, -1000) silicalite, and the ozone / trichlorobenzene molar ratio was set to 1.4. .
As test results, the outlet trichlorobenzene concentration, outlet O ₃ concentration, trichlorobenzene removal rate, and O ₃ removal rate are shown in Table 3 below.

処理液のトリクロロベンゼン濃度１０ｐｐｍ、オゾン濃度１５ｐｐｍで行った。

The treatment was performed at a trichlorobenzene concentration of 10 ppm and an ozone concentration of 15 ppm.

From Table 3, in the ozonolysis of trichlorobenzene, all of (S-1) to (S-5) are all in the SiO ₂ / Al ₂ O ₃ ratio 20 to 1000 (SiO ₂ / Al ₂ O ₃ ratio 1000). In USM, the removal rate is slightly higher than that of unfilled), which exceeds the decomposition rate of trichlorobenzene of unfilled Na-A. Although HCl, CO _{2 and the} like are generated by the reaction of the present invention, they are products of trichlorobenzene ozone reaction on the adsorbent, and the present invention is a high-performance trichlorobenzene removal method for advanced wastewater treatment facilities. It is shown that there is.

USY (SiO ₂ / Al ₂ O ₃ ratio 1000) showing the highest trichlorobenzene removal rate was made into a honeycomb and adsorbent shape-monolith (plate thickness 0.2 mm, pitch 2 mm), reaction temperature 25 ° C., ozone / treated substance The SV value was changed from 30 to 200 at a molar ratio of 1 (mol / mol), and the trichlorobenzene removal rate was evaluated.
FIG. 2 shows the relationship between the SV value and the trichlorobenzene removal rate.
It was confirmed that the trichlorobenzene removal rate was as high as 70% or higher in the entire range of SV values of 10 to 200, and when the SV value was set to 10, the removal rate of trichlorobenzene was 99% or higher.

USY (SiO ₂ / Al ₂ O ₃ ratio 1000) showing the highest trichlorobenzene removal rate was made into a honeycomb and adsorbent shape-monolith (plate thickness 0.2 mm, pitch 2 mm), reaction temperature 25 ° C., SV value 60, Then, the ozone / treatment substance molar ratio 1 (mol / mol) was changed from 0.5 to 3, and the trichlorobenzene removal rate was evaluated.
FIG. 3 shows the relationship between the ozone / treatment substance molar ratio and the trichlorobenzene removal rate.
The trichlorobenzene removal rate is high efficiency of 70% or more in the whole range of ozone / treatment substance molar ratio 1 (mol / mol) 0.5-3, and when the molar ratio is set to 2 or more, the trichlorobenzene removal rate is 99%. It was confirmed that

  It is applied to highly efficient treatment of trichlorobenzene from wastewater containing trichlorobenzene and groundwater containing trichlorobenzene discharged from the chemical industry, industrial waste treatment industry, and the like.

DESCRIPTION OF SYMBOLS 1 Main plant 2 Drainage discharge piping 3 Drainage transport pump 4 Mixer 5 Ozone generator 6 Adsorbent filling tower 6a Adsorbent layer 6b Ozone decomposition agent layer 6c Partition 7 Treatment liquid discharge piping

Claims (4)

(A) Add and mix ozone into the trichlorobenzene-containing liquid,
(B) The contained liquid adsorbs ozone and adsorbs trichlorobenzene (1) pentasil zeolite, (2) zeolite β, (3) ultrastable Y-type zeolite (USY), (4) mesoporous silicate, (5) flowing through a packed tower packed with at least one adsorbent selected from the group of ultrastable mordenite (USM);
(C) detoxify trichlorobenzene in the liquid by the action of ozone;
A method for treating a trichlorobenzene-containing liquid. (D) The method for treating a trichlorobenzene-containing liquid according to claim 1, wherein the treatment liquid obtained by detoxification in (C) is brought into contact with an ozone decomposing agent to decompose residual ozone. Adsorbs ozone and adsorbs trichlorobenzene (1) Pentasil zeolite, (2) Zeolite β, (3) Ultrastable Y-type zeolite (USY), (4) Mesoporous silicate, (5) Ultrastable mordenite (USM) ), An adsorbent packed tower provided with at least one adsorbent layer, a supply pipe for supplying a liquid containing trichlorobenzene to the adsorbent packed tower, connected to the supply pipe, and adding ozone to the liquid An apparatus for treating a trichlorobenzene-containing liquid, comprising: an ozone generator; and a discharge pipe for discharging the treated treatment liquid from the adsorbent packed tower. 4. The apparatus for treating a trichlorobenzene-containing liquid according to claim 3, wherein an ozone decomposing agent layer for decomposing leaking ozone is provided on the downstream side of the adsorbent packed tower.

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